Charging member, process cartridge and electrophotographic image forming apparatus

ABSTRACT

An electrophotographic charging member in which the adhesion of contamination is more suppressed is provided. The electrophotographic charging member includes an electro-conductive support and an electro-conductive elastic layer on the electro-conductive support, the electro-conductive elastic layer includes 10% by mass or more and 50% by mass or less of an aggregate of crosslinked rubber particles, the aggregate of the crosslinked rubber particles has a circle-equivalent diameter of 10 μm or more and 50 μm or less, the crosslinked rubber particles have one of an acrylic resin and a styrene acrylic resin chemically bonded to a surface thereof, the charging member has a protrusion derived from the aggregate of the crosslinked rubber particles on a surface thereof, and the protrusion has an average height of 50 nm or more and 200 nm or less.

BACKGROUND OF THE INVENTION

Field of the Invention

The present invention relates to a charging member, a process cartridgeand an electrophotographic image forming apparatus.

Description of the Related Art

In an electrophotographic image forming apparatus adopting a contactcharging method in which an electrophotographic photosensitive member(hereinafter also referred to as a “photosensitive member”) is chargedby a charging member disposed in contact with the electrophotographicphotosensitive member, toner remaining on the photosensitive member(hereinafter also referred to as “transfer residual toner”) may adhereto the surface of the charging member even after toner on thephotosensitive member is transferred to a paper or an intermediatetransfer member.

In addition, from the viewpoint of simplifying an electrophotographicimage forming apparatus and eliminating waste, a toner recycle system(hereinafter referred to as a “cleanerless system”) is proposed. In thesystem, a cleaning apparatus for removing transfer residual toner from aphotosensitive member is not provided, and transfer residual toner onthe photosensitive member is recovered by a developing apparatus.

When the contact charging method is adopted in the cleanerless system, alarger amount of transfer residual toner adheres to the surface of thecharging member.

As a means for reducing the adhesion of contamination substances such asan external additive and toner, Japanese Patent No. 5455336 and JapanesePatent Application Laid-Open No. 2008-83404 disclose a charging memberin which a fine particle is contained in a surface layer to controlsurface roughness and reduce adhesion.

One aspect of the present invention is directed to providing anelectrophotographic charging member in which the adhesion ofcontamination such as transfer residual toner is more suppressed. Inaddition, another aspect of the present invention is directed toproviding an electrophotographic image forming apparatus and a processcartridge which can stably form high quality electrophotographic imagesover a long period.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, there is provided acharging member including an electro-conductive support and anelectro-conductive elastic layer on the electro-conductive support,wherein the electro-conductive elastic layer includes 10% by mass ormore and 50% by mass or less of an aggregate of crosslinked rubberparticles, the aggregate of the crosslinked rubber particles has acircle-equivalent diameter of 10 μm or more and 50 μm or less, thecrosslinked rubber particles have one of an acrylic resin and a styreneacrylic resin chemically bonded to a surface thereof, the chargingmember has a protrusion derived from the aggregate of the crosslinkedrubber particles on a surface thereof, and the protrusion has an averageheight of 50 nm or more and 200 nm or less.

In addition, according to another aspect of the present invention, thereis provided an electrophotographic image forming apparatus including anelectrophotographic photosensitive member and the charging memberdisposed in contact with the electrophotographic photosensitive member.

Further, according to another aspect of the present invention, there isprovided a process cartridge configured to be attachable to anddetachable from a main body of an electrophotographic image formingapparatus, including an electrophotographic photosensitive member andthe charging member disposed in contact with the electrophotographicphotosensitive member.

Further features of the present invention will become apparent from thefollowing description of exemplary embodiments with reference to theattached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of one example of a chargingmember according to the present invention.

FIG. 2 is a diagram showing the height of a protrusion derived from anaggregate of crosslinked rubber particles.

FIG. 3 is an explanatory diagram for obtaining the average degree ofunevenness of the surface of an aggregate of crosslinked rubberparticles.

FIG. 4 is a schematic diagram of an apparatus used for the measurementof the electrical resistance value of a charging member.

FIG. 5 is a schematic cross-sectional view of one example of anelectrophotographic image forming apparatus according to the presentinvention.

FIG. 6 is a schematic cross-sectional view of one example of a processcartridge according to the present invention.

DESCRIPTION OF THE EMBODIMENTS

Preferred embodiments of the present invention will now be described indetail in accordance with the accompanying drawings.

The present invention will be described in detail below by aroller-shaped charging member (hereinafter also referred to as a“charging roller”) as one example of a charging member according to thepresent invention, but the present invention is not limited to theroller-shaped charging member.

The present inventors have confirmed that the charging members accordingto Japanese Patent No. 5455336 and Japanese Patent Application Laid-OpenNo. 2008-83404 achieve the effect of suppressing the adhesion of tonerand the like to the surface of the charging member. However, the presentinventors have recognized that in view of the adoption of theabove-described cleanerless system, further technical development isnecessary regarding the suppression of the adhesion of toner to thesurface of a charging member. Then, the present inventors have foundthat one of the main causes of contamination on the surface of acharging member in an electrophotographic image forming apparatusadopting the cleanerless system is due to toner positively charged.

As a result of further study based on the above analysis, the presentinventors have found that a charging member satisfying the following<Condition 1> and <Condition 2> is effective in the prevention orsuppression of the adhesion of contamination due to toner positivelycharged.

<Condition 1>

A electro-conductive elastic layer includes an aggregate of crosslinkedrubber particles having a circle-equivalent diameter of 10 μm or moreand 50 μm or less, and a charging member has a protrusion derived fromthe aggregate of the crosslinked rubber particles on the surfacethereof, and the average height of the protrusion is 50 nm or more and200 nm or less.

<Condition 2>

The crosslinked rubber particles have one of an acrylic resin and astyrene acrylic resin chemically bonded to the surface thereof.

The present inventors presume that the reason why the effect ofpreventing or suppressing the adhesion of transfer residual toner isobtained in a charging member satisfying the above <Condition 1> is asfollows: Due to the presence of the protrusion having an average heightof nm to 200 nm derived from the aggregate of the crosslinked rubberparticles, on the surface of the charging member, the contact areabetween transfer residual toner and the electro-conductive elastic layerreduces, and thus the transfer residual toner is more likely to roll onthe surface of the charging member. As a result, the transfer residualtoner is likely to be charged negativity due to friction with thesurface of the charging member and is less likely to adhere to thesurface of the charging member. Further, it is considered that theprotrusion is derived from the aggregate of the rubber particle, andtherefore contamination is likely to enter the gap between the rubberparticles of the rubber particle aggregate. Therefore, it is consideredthat contamination does not deposit on the surface of the rubberparticle aggregate constituting the protrusion, and the height of theprotrusion is less likely to change even in use for a long period, andthe rolling properties of toner is maintained over a long period.

In addition, by satisfying the above <Condition 2>, the adhesion ofcontamination substances is prevented or suppressed even when thecharging member is used in an electrophotographic image formingapparatus with high speed, high endurance and small particle diametertoner using a cleanerless system.

It is considered that the mechanism for achieving the above effect bythe above <Condition 2> is as follows: One of an acrylic resin and astyrene acrylic resin is chemically bonded to the surface of thecrosslinked rubber particles, and thus the tackiness of the surfacedecreases, and thus the rolling properties of transfer residual toner ina nip with a photosensitive member become better. Further, these resinsare chemically bonded to the surface, and thus the abrasion of thecrosslinked rubber particles constituting the protrusion is suppressedeven by image formation for a long period.

A charging member according to one aspect of the present invention willbe described in detail below by taking a charging member having a rollershape (hereinafter also referred to as a “charging roller”) as anexample.

[Charging Member]

FIG. 1 is a cross-sectional view of a charging roller according to oneaspect of the present invention in the direction orthogonal to the axisthereof. The charging roller has an electro-conductive substrate 1 andan electro-conductive elastic layer 2 laminated on the peripheralsurface thereof. In addition, the charging roller has a protrusionderived from an aggregate of crosslinked rubber particles on the surfacethereof. The average height of the protrusion derived from the aggregateof the crosslinked rubber particles is 50 nm or more and 200 nm or less.When the average height of the protrusion is 50 nm or more, toner can berolled, and tribo can be provided. When the average height of theprotrusion is 200 nm or less, the accumulation of contaminationsubstances on the surface of the charging roller can be suppressed. Theaverage height of the protrusion is more preferably 100 nm or more and200 nm or less.

[Physical Properties of Charging Member]

The charging member can usually have an electrical resistance value of1×10²Ω or more and 1×10¹⁰Ω or less in an environment of normaltemperature and normal humidity (a temperature of 23° C. and a relativehumidity of 50%) in order to make the charging of an electrophotographicphotosensitive member good. A method for measuring the electricalresistance value of a charging member is illustrated in FIG. 4. Bothends of the electro-conductive support of a charging member 7 arerotatably held by bearings 8 under loads. The charging member 7 areallowed to abut a cylindrical metal 9 having the same curvature as anelectrophotographic photosensitive member so as to be parallel to thecylindrical metal 9. While the cylindrical metal is rotated in the stateby a motor (not shown) to drive the abutting charging member to rotate,a direct current voltage of −200 V is applied to the charging memberfrom a stabilized power supply 10. The current flowing at the time ismeasured by an ammeter 11, and the electrical resistance value of thecharging member is calculated. The load applied to each one end of theelectro-conductive support is 4.9 N, the diameter of the cylindricalmetal is 30 mm, and the rotation speed is a peripheral speed of 45mm/sec.

The electro-conductive elastic layer can have a shape in which the outerdiameter of the central portion in the longitudinal direction is thelargest, and the outer diameter decreases along the directions of bothends in the longitudinal direction, the so-called crown shape, in orderto make the width of a nip extending in the longitudinal direction withrespect to a photosensitive member more uniform. As the amount of thecrown, the difference between the outer diameter of the central portionin the longitudinal direction and the average value of outer diametersat two points on the left and right at positions 90 mm away from thecentral portion can be 30 μm or more and 200 μm or less. By setting theamount of the crown in the range, the state of contact between thecharging member and an electrophotographic photosensitive member can bemade more stable.

The hardness of the electro-conductive elastic layer is preferably 90°or less, more preferably 40° or more and 80° or less, in terms ofmicrohardness (model MD-1). By setting the microhardness at 90° or less,in particular at 40° or more and 80° or less, it is easy to stabilizeabutting a photosensitive member, and the photosensitive member can bemore stably charged.

The microhardness (model MD-1) is hardness measured by pressing anindenter against the outer surface of the electro-conductive elasticlayer using a micro rubber hardness meter (trade name: MD-1 capa;manufactured by Kobunshi Keiki Co., Ltd.). Specifically, the hardness ismeasured in a peak hold mode at 10 N with the indenter allowed to abutthe surface of the electro-conductive elastic layer of the chargingmember that has been allowed to stand in an environment of normaltemperature and normal humidity (a temperature of 23° C. and a relativehumidity of 50%) for 12 hours or more. For the indenter, type A (height0.50 mm, diameter 0.16 mm, cylindrical shape) is used. A portion otherthan the protrusion derived from the rubber particle aggregate isselected, and the indenter is allowed to abut the portion.

The hardness of the electro-conductive elastic layer can be adjusted bythe type and amount of a vulcanizing agent included in a materialmixture for electro-conductive elastic layer formation, the type andamount of a vulcanization aid, vulcanization temperature, vulcanizationtime and the content of a filler.

[Electro-Conductive Support]

The electro-conductive support has electro-conductivity and has thefunction of supporting a resin layer provided thereon. Examples of thematerial of the electro-conductive support can include metals such asiron, copper, aluminum and nickel, and alloys thereof (stainless steeland the like). In addition, for the purpose of providing scratchresistance, the surfaces of these may be subjected to plating treatmentin a range that does not impair electro-conductivity. Further, as theelectro-conductive support, a resin substrate having the surface coatedwith a metal, and a substrate produced from an electro-conductive resincomposition can also be used.

[Electro-Conductive Elastic Layer]

<Binder>

As the binder constituting the electro-conductive elastic layer, a knownrubber, elastomer, or resin can be used. From the viewpoint of ensuringa sufficient nip between the charging member and a photosensitivemember, the electro-conductive elastic layer can have relatively lowelasticity, and a rubber is suitably used as the binder. Examples of therubber can include a natural rubber, a synthetic rubber, or rubbersobtained by vulcanizing and crosslinking these.

Examples of the synthetic rubber include the following rubbers: anethylene propylene rubber, a styrene butadiene rubber (SBR), a siliconerubber, a urethane rubber, an isoprene rubber (IR), a butyl rubber, anacrylonitrile butadiene rubber (NBR), a chloroprene rubber (CR), anacrylic rubber, an epichlorohydrin rubber and a fluororubber.

<Crosslinked Rubber Particle>

Examples of the rubber particles constituting the aggregate of thecrosslinked rubber particles include particles including the followingrubbers: a polyurethane rubber, a silicone rubber, a butadiene rubber,an isoprene rubber, a chloroprene rubber, a styrene-butadiene rubber(SBR), an ethylene-propylene rubber, a polynorbornene rubber, anacrylonitrile rubber (NBR) and an epichlorohydrin rubber.

Particularly, crosslinked rubber particles including either one or bothof an acrylonitrile rubber and a styrene-butadiene rubber isparticularly preferred because the effect of suppressing theenergization deterioration of the charging member is large.

The primary particle diameter of the crosslinked rubber particles can be100 nm or more and 1000 nm or less. When the primary particle diameteris 100 nm or more, the deposition of contamination on the chargingmember is reduced. When the primary particle diameter is 1000 nm orless, toner can be charged negatively by rolling in a nip to providetribo to the toner. The primary particle diameter of the crosslinkedrubber particles is measured, for example, in terms of average particlediameter based on the CONTIN method using a thick type particle diameteranalyzer (trade name: FPAR-1000, manufactured by Otsuka Electronics Co.,Ltd.).

[Method for Preparing Crosslinked Rubber Particles]

The crosslinked rubber particles can be produced by polymerizing a rawmaterial mixture including a monomer for a rubber, a crosslinking agent,a graft crossing agent, a polymerization initiator, an emulsifier andthe like by a known method such as emulsion polymerization. A latexincluding crosslinked rubber particles is produced by emulsionpolymerization.

The monomer for a rubber is not particularly limited. Examples thereofinclude the following monomers: 1-3 butadiene, isoprene(2-methyl-1,3-butadiene), chloroprene (2-chloro-1,3-butadiene), styrene,ethylene, propylene, acrylonitrile, norbornene, epichlorohydrin,ethylene oxide and allyl glycidyl ether. When the monomer for a rubberhas two or more unsaturated double bonds in the molecule thereof (forexample, 1,3-butadiene and isoprene (2-methyl-1,3-butadiene) and thelike), the crosslinking agent and the graft crossing agent are notalways necessary.

The crosslinking agent is not particularly limited. Examples thereofinclude sulfur and peroxides. The graft crossing agent is notparticularly limited. Examples thereof include allyl methacrylate,triallyl cyanurate and triallyl isocyanurate.

The polymerization initiator is not particularly limited. Examplesthereof include the following: water-soluble persulfuric acid salts suchas potassium persulfate, sodium persulfate and ammonium persulfate; andorganic peroxides such as diisopropylbenzene hydroperoxide, p-menthanehydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide andmethylcyclohexyl hydroperoxide. One of these polymerization initiatorscan be used alone, or two or more of these polymerization initiators canbe used in combination.

The emulsifier is not particularly limited. Examples thereof include thefollowing: alkali metal salts of higher fatty acids such asdisproportionated rosin acid, oleic acid and stearic acid; sulfonicacid-based salt compounds such as sodium dodecylbenzenesulfonate andsodium alkyl diphenyl ether disulfonate; and sulfuric acid-based saltcompounds such as sodium lauryl sulfate. One of these emulsifiers can beused alone, or two or more of these emulsifiers can be used incombination.

[Chemical Bond to Particle Surface]

The crosslinked rubber particles constituting the aggregate of thecrosslinked rubber particles have one of an acrylic resin and a styreneacrylic resin chemically bonded to the surface thereof. Thus, thetackiness of the surface of the aggregate of the crosslinked rubberparticles is reduced, and the strength of the surface of the aggregateof the crosslinked rubber particles is kept, and thus the durabilitywhen the charging member is used in an image forming apparatus improves.In addition, the accumulation of toner and an external additive on thesurface of the electro-conductive elastic layer is suppressed, andtherefore the contamination on the charging member can be suppressed.The form of the chemical bond can be a chemical bond by graftpolymerization.

The graft polymerization can be carried out by adding a monomer mixedliquid for graft polymerization to a latex including crosslinked rubberparticles obtained by the emulsion polymerization method, and performingpolymerization by a known method. Thus, crosslinked rubber particleshaving one of an acrylic resin and a styrene acrylic resin chemicallybonded to the surface (hereinafter also referred to as a “resin-coatedcrosslinked rubber particle”) are produced. The method for confirmingthe presence or absence of a chemical bond will be described later.

[Acrylic Resin and Styrene Acrylic Resin]

Examples of the acrylic resin chemically bonded to the surface of thecrosslinked rubber particles include a polymer obtained by polymerizingone or more monomers selected from the group consisting of acrylic acid,methacrylic acid, an acrylate and a methacrylate. Particularly, anacrylic resin obtained by polymerizing acrylic acid or methacrylic acidis suitably used.

Examples of the acrylic resin include a polymethacrylate such aspolymethyl methacrylate, and a methacrylic copolymer including as a maincomponent a methacrylate unit such as methyl methacrylate. Specificexamples of the methacrylic copolymer include a copolymer of methylmethacrylate and a copolymerizable vinyl monomer.

Examples of the copolymerizable vinyl monomer include (meth)acrylatesother than methyl methacrylate, such as methyl acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate,2-ethylhexyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate, andaromatic vinyl monomers such as styrene.

In addition, examples of the styrene acrylic resin chemically bonded tothe surface of the crosslinked rubber particles include copolymersobtained by copolymerizing by a known method components mentioned below:styrene; styrene-based monomers such as α-methylstyrene,o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene,p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene,p-tert-butylstyrene, n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene,p-n-decylstyrene, p-n-dodecylstyrene and p-phenylstyrene; acrylates suchas methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate,n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexylacrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate and2-hydroxyethyl acrylate; methacrylates such as methyl methacrylate,ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate,isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate,2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate anddiethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile andacrylamide; sulfonic acids such as styrenesulfonic acid,2-acrylamido-2-methylpropanesulfonic acid,2-methacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid andmethacrylsulfonic acid; and maleic acid amide derivatives, maleimidederivatives, and styrene derivatives.

In the crosslinked rubber particles having one of an acrylic resin and astyrene acrylic resin chemically bonded to the surface, the proportionof the acrylic resin and/or the styrene acrylic resin chemically bondedto the surface to 100 parts by mass of the crosslinked rubber particlesbefore one of the acrylic resin and the styrene acrylic resin ischemically bonded to the surface (hereinafter also referred to as an“untreated crosslinked rubber particles”) is not particularly limitedbut can be 10 parts by mass or more and 30 parts by mass or less. Whenthe proportion is 10 parts by mass or more, the rolling properties oftoner and the durability of the rubber particle improve. When theproportion is 30 parts by mass or less, the flexibility of thecrosslinked rubber particles is kept, and scraping theelectrophotographic photosensitive member can be suppressed.

<Aggregate of Crosslinked Rubber Particles>

The aggregate of the crosslinked rubber particles is an aggregate ofcrosslinked rubber particles each of which is a primary particle, and isthe so-called secondary particle. Here, the crosslinked rubber particlehas one of an acrylic resin and a styrene acrylic resin chemicallybonded to the surface. It is considered that by providing on the surfaceof the charging member the protrusion derived from the aggregate of thecrosslinked rubber particles each of which is a primary particle,contamination adhering to the protrusion is likely to be incorporatedinto the aggregate of the crosslinked rubber particles. Therefore, it isconsidered that the accumulation of contamination substances on theprotrusion is suppressed.

The aggregate of the crosslinked rubber particles can be obtained as apowder by dropping a latex including the resin-coated crosslinked rubberparticles into a liquid including a coagulant to aggregate and solidifythe crosslinked rubber particles followed by separation, washing anddrying. As these aggregation and solidification to drying methods, knownmethods can be used. Examples of the coagulant include metal salts suchas calcium acetate, aluminum sulfate and calcium chloride, and inorganicacids such as sulfuric acid, hydrochloric acid, phosphoric acid andnitric acid.

[Particle Diameter of Aggregate of Crosslinked Rubber Particles]

The particle diameter of the aggregate of the crosslinked rubberparticles is 10 μm or more and 50 μm or less in terms ofcircle-equivalent diameter. When the particle diameter is 10 μm or more,rolling properties can be provided to toner. When the particle diameteris 50 μm or less, the adhesion of contamination substances to thesurface of the charging member can be suppressed. The circle-equivalentdiameter can be obtained by observing a cross section of theelectro-conductive elastic layer by a microscope or the like.Specifically, a cross section of the electro-conductive elastic layer isobserved by a transmission electron microscope (TEM), the projected areaof the aggregate of the crosslinked rubber particles is obtained fromimage data of a cross section of the aggregate of the crosslinked rubberparticles, and the circle-equivalent diameter is calculated from thearea.

[Content of Aggregate of Crosslinked Rubber Particles]

The content of the aggregate of the crosslinked rubber particles in theelectro-conductive elastic layer is 10% by mass or more and 50% by massor less. When the content of the aggregate of the crosslinked rubberparticles is 10% by mass or more, tribo providing properties to tonerare exhibited. When the content of the aggregate of the crosslinkedrubber particles is 50% by mass or less, the adhesion of contaminationsubstances due to the deposition of an external additive of toner andthe like can be suppressed on the surface of the charging member.

[Average Degree of Unevenness]

The surface of the aggregate of the crosslinked rubber particles has aminute protrusion shape. The average degree of unevenness of theaggregate of the crosslinked rubber particles can be measured byobserving the surface of the charging member in the range of a field ofview of 0.5 mm×0.5 mm using a laser microscope (trade name: LSM5 PASCAL;manufactured by Carl Zeiss). A specific measurement method is asfollows.

The wavelength of the laser to be excited is changed, and the spectrumof the excitation light is examined to identify whether the protrusionin the field of view is derived from the aggregate of the crosslinkedrubber particles or another particles. Scanning is performed in the X-Yplane in the field of view with a laser to obtain two-dimensional imagedata. From the obtained image data, the protrusion derived from theaggregate of the crosslinked rubber particles is cut from the apex ofthe protrusion in a direction parallel to the Z direction and parallelto the longitudinal direction of the charging member by a sharp-edgedcutting tool (a razor blade, a utility knife or the like), a microtomeor the like. The cut cross section is observed by an optical microscopeor an electron microscope to obtain image data of the cross section ofthe aggregate of the crosslinked rubber particles. For the obtainedimage data, the ratio “A/B” of “actual cross-sectional peripherallength” A to “envelope peripheral length” B of the aggregate of thecrosslinked rubber particles is obtained using image analysis software(trade name: Image-PRO Plus, manufactured by Planetron, Inc.), and theratio is taken as the degree of unevenness (see FIG. 3).

Here, the “envelope peripheral length” refers to circumferential lengthwhen the protrusions in the cross section of the aggregate of thecrosslinked rubber particles are connected (numeral 5 in FIG. 3). Suchwork is performed for protrusions derived from 10 aggregates of thecrosslinked rubber particles, and the arithmetic mean of the 10 degreesof unevenness obtained is taken as the average degree of unevenness. Theaverage degree of unevenness can be 1.10 or more and 1.30 or less. Whenthe average degree of unevenness is 1.10 or more, the rolling providingproperties to toner become good, and the tribo providing properties canbe improved. In addition, when the average degree of unevenness is 1.30or less, the collapse of the aggregate of the crosslinked rubberparticles into the primary particle can be suppressed.

[Average Height of Protrusion]

The surface of the charging member according to one aspect of thepresent invention has a protrusion derived from an aggregate of acrosslinked rubber particles, and the average height of the protrusionis 50 nm or more and 200 nm or less. When the average height of theprotrusion is 50 nm or more, the rolling properties of transfer residualtoner on the surface of the charging member improve, and the negativecharge providing properties to transfer residual toner improve. Inaddition, when the average height of the protrusion is 200 nm or less,the adhesion of contamination substances to the surface of the chargingmember can be suppressed.

The height of the protrusion (numeral 3 in FIG. 2) can be specificallymeasured, for example, by the following method. The surface of theelectro-conductive elastic layer of the charging member is observed in afield of view of 0.5 mm×0.5 mm using a laser microscope (trade name:LSM5 PASCAL, manufactured by Carl Zeiss) as a measuring instrument. Thewavelength of the laser to be excited is changed, and the spectrum ofthe excitation light is examined to identify whether the protrusion inthe field of view is derived from the aggregate 4 of the crosslinkedrubber particles or another additives or the like. Then, scanning isperformed in the X-Y plane in the field of view with a laser to furtherdetect the protrusion of the aggregate of the crosslinked rubberparticles from two-dimensional image data. The work is performed for 10aggregates of the crosslinked rubber particles in the field of view.

In addition, the above measurement is performed in each of 10 regionsobtained by dividing the longitudinal direction of the charging memberat generally equal intervals into 10 parts. With the apexes of theprotrusions of a total of 100 aggregates of the crosslinked rubberparticles obtained and the planar portion of the surface of theelectro-conductive elastic layer as a reference plane, the heights ofthe protrusions of the aggregates of the crosslinked rubber particlesare calculated. The average value of the heights of the 100 protrusionscalculated is taken as “the average height of the protrusion.”

<Electro-Conductive Material>

A known electro-conductive material can be contained in theelectro-conductive elastic layer. Examples of the electro-conductivematerial include an electron-conductive agent and an ion-conductiveagent.

Examples of the electron-conductive agent include the following: fineparticles and fibers based on metals such as aluminum, palladium, iron,copper and silver; metal oxides such as titanium oxide, tin oxide andzinc oxide; composite materials obtained by surface-treating thesurfaces of the metal-based fine particles and fibers and metal oxidesby electrolytic treatment, spray coating or mixing and shaking; andcarbon black and carbon-based fine particles.

Examples of the carbon black can include furnace black, thermal black,acetylene black and keten black. Examples of the furnace black includethe following: SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, I-ISAF-HS, HAF-HS,HAF, HAF-LS, T-HS, T-NS, MAF, FEF, GPF, SRF-HS-HM, SRF-LM, ECF andFEF-HS. Examples of the thermal black can include FT and MT. Examples ofthe carbon-based fine particles can include PAN(polyacrylonitrile)-based carbon particles and pitch-based carbonparticles.

The surface of the electron-conductive agent may be treated with asurface treatment agent. As the surface treatment agent, organosiliconcompounds such as alkoxysilanes, fluoroalkylsilanes and polysiloxanes,various coupling agents based on silane, titanates, aluminates andzirconates, oligomers or polymer compounds can be used. One of these canbe used alone, or two or more of these can be used in combination. Asthe surface treatment agent, organosilicon compounds such asalkoxysilanes and polysiloxanes, and various coupling agents based onsilane, titanates, aluminates or zirconates are preferred, andorganosilicon compounds are further preferred.

When the electro-conductive material is a fine particle, the averageparticle diameter of the fine particle is more preferably 0.01 μm ormore and 0.9 μm or less, further preferably 0.01 μm or more and 0.5 μmor less.

Examples of the ion-conductive agent include the following: inorganicion substances such as lithium perchlorate, sodium perchlorate andcalcium perchlorate; cationic surfactants such aslauryltrimethylammonium chloride, stearyltrimethylammonium chloride,octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride,hexadecyltrimethylammonium chloride, trioctylpropylammonium bromide andmodified aliphatic dimethylethylammonium ethosulfate; zwitterionicsurfactants such as lauryl betaine, stearyl betaine anddimethylalkyllauryl betaine; quaternary ammonium salts such astetraethylammonium perchlorate, tetrabutylammonium perchlorate andtrimethyloctadecylammonium perchlorate; and organic acid lithium saltssuch as lithium trifluoromethanesulfonate. One of these can be usedalone, or two or more of these can be used in combination. When thebinder is a polar rubber, particularly an ammonium salt can be used.

<Other Components>

In addition, an additive such as a softening oil or a plasticizer, or aninorganic particle may be contained in the electro-conductive elasticlayer in order to adjust hardness.

Examples of the inorganic particle include the following: particles ofzinc oxide, tin oxide, indium oxide, titanium oxide (titanium dioxide,titanium monoxide and the like), iron oxide, silica, alumina, magnesiumoxide, zirconium oxide, strontium titanate, calcium titanate, magnesiumtitanate, barium titanate, calcium zirconate, barium sulfate, molybdenumdisulfide, calcium carbonate, magnesium carbonate, dolomite, talc,kaolin clay, mica, aluminum hydroxide, magnesium hydroxide, zeolite,wollastonite, diatomaceous earth, glass beads, bentonite,montmorillonite, hollow glass spheres, organometallic compounds andorganometallic salts.

In addition, iron oxides such as ferrite, magnetite and hematite, andactivated carbon can also be used. One of these electro-conductivematerials can be used alone, or two or more of these electro-conductivematerials can be used in combination.

[Electrophotographic Image Forming Apparatus]

An electrophotographic image forming apparatus according to one aspectof the present invention includes an electrophotographic photosensitivemember and a charging member disposed in contact with theelectrophotographic photosensitive member, and as the charging member,the charging member according to the present invention is used. Theschematic configuration of one example of the electrophotographic imageforming apparatus is illustrated in FIG. 5. The electrophotographicimage forming apparatus includes an electrophotographic photosensitivemember, a charging apparatus, an exposure apparatus, a developingapparatus, a transfer apparatus, a fixing apparatus and the like.

An electrophotographic photosensitive member 12 is a rotary drum typephotosensitive member having a photosensitive layer on anelectro-conductive support. The electrophotographic photosensitivemember 12 is rotationally driven in a direction shown by an arrow at apredetermined peripheral speed (process speed). The charging apparatushas a contact type charging member (charging roller) 7 disposed incontact by being allowed to abut the electrophotographic photosensitivemember 12 with a predetermined pressing pressure. The charging member 7is driven to rotate according to the rotation of the electrophotographicphotosensitive member 12. In addition, a predetermined direct currentvoltage is applied to the charging member 7 from a charging power supply14, and the electrophotographic photosensitive member 12 can be chargedto a predetermined potential. By irradiating the electrophotographicphotosensitive member 12 uniformly charged by the charging apparatuswith exposure light 15 corresponding to image information from a latentimage forming apparatus (not shown), an electrostatic latent image isformed. For the latent image forming apparatus, for example, an exposureapparatus such as a laser beam scanner is used.

The developing apparatus has a developing sleeve or developing roller 13disposed in proximity to or in contact with the electrophotographicphotosensitive member 12. With toner electrostatically treated to thesame polarity as the charging polarity of the electrophotographicotosensitive member 12, the electrostatic latent image is developed byreversal development to form a toner image. The transfer apparatus has acontact type transfer roller 16. The toner image is transferred from theelectrophotographic photosensitive member 12 to a transfer material 17such as plain paper. The transfer material is conveyed by a paper feedsystem having a conveying member. Here, in the electrophotographic imageforming apparatus of the present invention, a cleanerless system inwhich transfer residual toner is recovered by a developing apparatus isadopted, and therefore no cleaning apparatus is present. A fixingapparatus 18 includes a heated roll and the like, and the transferredtoner image is fixed to the transfer material 17, and the transfermaterial 17 is discharged out of the machine. The above is a series ofelectrophotographic processes.

[Process Cartridge]

The schematic configuration of one example of a process cartridge isillustrated in FIG. 6. In the process cartridge, an electrophotographicphotosensitive member 102, a charging roller 101, a developing roller103, a cleaning member 106 are integrated, and the process cartridge isconfigured to be attachable to and detachable from the main body of anelectrophotographic image forming apparatus. The charging memberaccording to one aspect of the present invention can be used as thecharging roller of the process cartridge.

According to one aspect of the present invention, a charging member inwhich the adhesion of contamination substances to the surface is reducedcan be obtained. In addition, according to another aspect of the presentinvention, an electrophotographic image forming apparatus and a processcartridge that can stably form high quality electrophotographic imagescan be obtained.

EXAMPLES

The present invention will be described in more detail below by givingspecific examples, but the technical scope of the present invention isnot limited to these. Commercial raw materials and reagents were usedfor materials not particularly described below. In addition, the unitsof amounts blended are parts by mass and % by mass unless otherwisedescribed. An evaluation method regarding a chemical bond to thesurfaces of crosslinked rubber particles is as follows.

1. Measurement of Graft Ratio

The amount (graft ratio) of an acrylic resin or a styrene acrylic resinchemically bonded to the surface of crosslinked rubber particles bygraft polymerization was confirmed by the following method.

2.5 g of resin-coated crosslinked rubber particles and 100 ml of acetonewere placed in a container, heated at 23° C. for 3 hours, and thencentrifuged at 10000 rpm for 60 minutes using a centrifuge (H-2000B,rotor H, manufactured by KOKUSAN Co. Ltd.), and acetone-insoluble matterwas recovered. Then, the acetone-insoluble matter was dried, the mass ofthe acetone-insoluble matter S was measured, and the graft ratio wasobtained by the following formula:graft ratio(% by mass)=[(S−G)/G]×100wherein G is the mass of the crosslinked rubber particles included in2.5 g of the resin-coated crosslinked rubber particles, calculated fromthe ratio between the mass of the crosslinked rubber particles used ingraft polymerization and the mass of the produced resin-coatedcrosslinked rubber particles.

Production Example 1

<Step 1>

An autoclave (practical pressure resistance 0.6 NpaG) was charged withthe materials shown in the Component (1) column in the following Table1, and the atmosphere in the autoclave was replaced by nitrogen.Subsequently, Component (2) in the following Table 1 was added to theautoclave. Then, the temperature was increased while the obtained mixedliquid was stirred, and at a point of time when the liquid temperaturereached 45° C., a mixture of the materials shown in the Component (3)column in Table 1 was introduced into the autoclave, and the temperaturewas increased to 60° C. Then, at a point of time when the polymerizationconversion rate in the above solution reached 97%, the polymerizationwas completed to obtain butadiene rubber polymer latex No. 1. The solidsof the obtained butadiene rubber polymer latex accounted for 40%.

TABLE 1 Material Parts by mass Component Styrene 25 (1) Paramenthanehydroperoxide 0.3 Na pyrophosphate (anhydrous) 0.15 Potassium tallowate1.5 Deionized water 140 Component 1,3-Butadiene 75 (2) Component Ferroussulfate heptahydrate 0.003 (3) Hydrous crystal glucose 0.2 Deionizedwater 10

<Step 2>

The materials shown in the Component (4) column in the following Table 2were placed in a reactor, and the atmosphere in the reactor was replacedby nitrogen. Then, the material shown in the Component (5) column wasadded to the reactor, and the liquid temperature was increased to 70° C.Then, a mixture of the materials shown in the Component (6) column inTable 2 was added to the reactor over 30 minutes, and the state wasmaintained for 100 minutes. Then, a mixture of the materials shown inthe Component (7) column in Table 2 was added to the reactor over 30minutes, and the state was maintained for 120 minutes to completepolymerization.

TABLE 2 Material Parts by mass Component Butadiene rubber polymer latexNo. 1 583 (4) (Solids 233) Deionized water 85 Potassium tallowate 5.0Component Sodium formaldehyde sulfoxylate 0.3 (5) dihydrate ComponentMethyl methacrylate 28 (6) Ethyl acrylate 7 Cumene hydroperoxide 0.15Component Methyl methacrylate 10 (7) Cumene hydroperoxide 0.05

The latex of the graft copolymer thus obtained was dropped into 200parts of hot water in which 5.0% by mass of calcium acetate wasdissolved to solidify the graft copolymer, and the graft copolymer wasseparated, washed, and dried at 75° C. for 16 hours to obtain particlesof powdery butadiene rubber-based graft copolymer. The particles wereparticle No. 1.

The primary particle diameter, circle-equivalent diameter and averagedecree of unevenness of particle No. 1 were measured according to theabove-described methods. In addition, particle No. 1 was an aggregate ofa crosslinked rubber particles each of which was a primary particle.

Further, the fact that the crosslinked rubber particles constitutingparticle No. 1 had an acrylic resin chemically bonded to the surface wasconfirmed by the above-described method. Further, the graft ratio of theacrylic resin onto the crosslinked rubber particles was by mass. Themeasurement results are shown in Table 7.

Production Examples 2 and 3

The reaction temperature in <Step 1> of Production Example 1 was chancedfrom 60° C. to 50° C. or 70° C. Except for the change, butadiene rubberpolymer latexes No. 2 and No. 3 were prepared as in <Step 1> ofProduction Example 1. Then, particle No. 2 and particle No. 3 were madeas in <Step 2> of Production Example 1 except that the obtainedbutadiene rubber polymer latex No. 2 or No. 3 was used.

Production Examples 4 and 5

Butadiene rubber polymer latexes No. 4 and No. 5 were prepared as in<Step 1> of Production Example 1 except that the amount of deionizedwater added in <Step 1> of Production Example 1 was changed from 140parts to 200 parts or 100 parts. Then, particle No. 4 and particle No. 5were made as in <Step 2> of Production Example 1 except that theobtained butadiene rubber polymer latexes No. 4 and No. 5 were used.

Production Examples 6 and 7

In Production Example 1, the amount of “paramenthane hydroperoxide”blended in Component (1) in Table 1 was changed to 0.1 parts by mass or0.6 parts by mass. Except for the change, butadiene rubber polymerlatexes No. 6 and No. 7 were prepared as in <Step 1> of ProductionExample 1. Then, particle No. 6 and particle No. 7 were made as in <Step2> of Production Example 1 except that the obtained butadiene rubberpolymer latexes No. 6 and No. 7 were used.

Production Example 8

<Step 3>

[Step 3-1]

A mixture of the materials shown in the Component (9) column in thefollowing Table 3 was added to 10 parts of butadiene rubber polymerlatex No. 1 prepared in Production Example 1 (4 parts of solids), andthe liquid temperature was increased to 70° C.

[Step 3-2]

Then, a mixture of the materials shown in the Component (10) column inTable 3 was added over 180 minutes, and the mixture was reacted at atemperature of 70° C. for 120 minutes to complete graft polymerization.

TABLE 3 Material Parts by mass Component Butadiene rubber polymer latexNo. 1 10 (9) Deionized water 9.0 Sodium dodecylbenzenesulfonate 0.9Component Acrylonitrile 27 (10) Styrene 63 n-Octyl mercaptan 1.8

The solids of the obtained graft copolymer latex No. 8 accounted for40%. The latex of the graft copolymer was dropped into 200 parts of hotwater in which 5.0% by mass of calcium acetate was dissolved to solidifythe graft copolymer, and the graft copolymer was separated, washed, anddried at 75° C. for 16 hours to obtain particles of powdery butadienerubber-based graft copolymer. The particles were particle No. 8.

Production Examples 9 and 10

The liquid temperature in [Step 3-1] of Production Example 8 was changedfrom 70° C. to 60° C. or 80° C. Except for the change, graft polymerlatexes No. 9 and No. 10 were prepared as in <Step 3> of ProductionExample 8. Then, particle No. 9 and particle No. 10 were made as in<Step 3> of Production Example 8 except that graft polymer latexes No. 9and No. 10 were used.

Production Examples 11 and 12

Particle No. 11 and particle No. 12 were made as in Production Example 8except that the butadiene latex obtained in Step 1 of Production Example4 or the butadiene latex obtained in Step 1 of Production Example 5 wasused instead of “butadiene rubber polymer latex No. 1” in ProductionExample 8.

Production Examples 13 and 14

Particle No. 13 or particle No. 14 was made as in Production Example 8except that the butadiene rubber polymer latex obtained in ProductionExample 6 or 7 was used instead of “butadiene rubber polymer latex No.1” in Production Example 8. The evaluation results are shown in Table 7.

Production Example 15

<Step 4>

[Step 4-1]

A separable flask equipped with a condenser and a stirring blade wascharged with the materials shown in the Component (11) column in thefollowing Table 4, and the liquid temperature was increased to 80° C.Subsequently, the atmosphere in the flask was replaced by nitrogen with200 ml/min of a nitrogen gas flow for 50 minutes, the material shown inthe Component (12) column in Table 4 was added, and the mixture wasallowed to stand for 5 minutes. Then, a mixture of the materials shownin the Component (13) column in Table 4 was placed in the flask over 10minutes, and a liquid temperature of 80° C. was maintained for 100minutes to complete the first-stage polymerization step for theproduction of a crosslinked rubber particle aggregate 15.

[Step 4-2]

Subsequently, a mixed liquid of the materials shown in the Component(14) column in Table 4 was introduced, and the mixture was allowed tostand for 5 minutes. Then, the material shown in the Component (15)column in Table 4 was added, and a mixed liquid of the materials shownin the Component (16) column in Table 4 was further dropped over 200minutes. In the polymerization, the material shown in the Component (17)column in Table 4 was added three times, 45 minutes, 90 minutes and 125minutes after the start of the dropping. The amount of the materialshown in the Component (17) column in Table 4 added was 0.05 parts eachtime. Thus, the total amount added was 0.150 parts.

After the completion of the dropping, a liquid temperature of 80° C. wasmaintained for 150 minutes to complete the second-stage polymerizationstep to obtain a latex of a rubbery polymer (A) [polyalkyl(meth)acrylate-based composite rubber]. The polymerization rate of therubbery polymer (A) was 99.9%. In addition, the solids of the latexaccounted for 92.7%.

TABLE 4 Parts by Material mass Component Boric acid 0.3 (11) Sodiumcarbonate 0.03 Deionized water 200 Component Potassium persulfate 0.7(12) Component n-Butyl acrylate 10 (13) Allyl methacrylate 0.5 n-Octylmercaptan 0.5 Component Ferrous sulfate 0.002 (14) Disodiumethylenediaminetetraacetate salt 0.006 Sodium hydroxymethanesulfinatedihydrate 0.1 (Rongalite) Deionized water 5 Component Sodium laurylsulfate 0.05 (15) Component n-Butyl acrylate 75 (16) Allyl methacrylate0.375 tert-Butyl peroxide 0.075 Component Sodium lauryl sulfate 0.150(17)

<Step 5> Graft Polymerization

The temperature of the latex of the rubbery polymer (A) was decrease to65° C., and the system was charged with a mixture of other materialsshown in the Component (18) column in the following Table 5.Subsequently, a mixture of the materials shown in the Component (19)column in Table 5 was further introduced into the system to performgraft polymerization. Subsequently, the state was maintained for 150minutes to complete the polymerization to obtain a latex of an acrylicrubber-based graft copolymer including the rubbery polymer (A) and agraft portion (B). The latex of the graft copolymer was dropped into 200parts of hot water in which 5.0% by mass of calcium acetate wasdissolved to solidify the graft copolymer, and the graft copolymer wasseparated, washed, and dried at 75° C. for 16 hours to obtain particlesof powdery acrylic rubber-based graft copolymer. The particles wereparticle No. 15. Particle No. 15 was an aggregate of crosslinked rubberparticles each of which was a primary particle.

TABLE 5 Parts by Material mass Component Latex of rubbery polymer (A) 75(18) Methyl methacrylate 13 Butyl acrylate 2 Allyl methacrylate 0.15Component Sodium lauryl sulfate 0.05 (19) Sodium hydroxymethanesulfinatedihydrate 0.05 (Rongalite) Deionized water 10

Production Examples 16 and 17

Particle No. 16 and particle No. 17 were made as in <Step 4> and <Step5> of Production Example 15 except that the reaction temperature in[Step 4-1] of Production Example 15 was changed from 80° C. to 70° C. or90° C.

Production Examples 18 and 19

The number of parts of the added deionized water in Component (11) in[Step 4-1] of Production Example 15 was changed to 300 parts or 100parts, and the holding time after the mixture of the materials shown inthe Component (13) column was added to the flask, in [Step 4-1], waschanged from 100 minutes to 240 minutes. Except for the changes, latexeswere prepared as in <Step 4> of Production Example 15. Then, particleNo. 18 and particle No. 19 were made as in <Step 5> of ProductionExample 15 except that the obtained latexes were used.

Production Examples 20 and 21

The conditions of the polymerization step in [Step 4-2] of ProductionExample 15 were changed from a temperature of 80° C. and a time of 150minutes to a temperature of 70° C. and a time of 100 minutes or atemperature of 80° C. and a time of 240 minutes. Except for the changes,latexes were prepared as in <Step 4> of Production Example 15. Then,particle No. 20 and particle No. 21 were made as in <Step 5> ofProduction Example 15 except that these latexes were used.

Production Example 22

The latex of the rubbery polymer (A) prepared in <Step 4> of ProductionExample 15 was provided. Particle No. 22 was made as in <Step 3-1> and<Step 3-2> of Production Example 8 except that the latex was used.

Production Examples 23 and 24

Latexes were prepared as in <Step 4> of Production Example 15 exceptthat the reaction temperature in the first-stage polymerization step in[Step 4-1] of Production Example 15 was changed from 80° C. to 70° C. or90° C. Particle No. 23 and particle No. 24 were made as in <Step 3-1>and <Step 3-2> of Production Example 8 except that these latexes wereused.

Production Examples 25 and 26

The latexes prepared in Production Example 18 and Production Example 19were provided. Particle No. 25 and particle No. 26 were made as in <Step3-1> and <Step 3-2> of Production Example 8 except that these latexeswere used.

Production Examples 27 and 28

The latexes prepared in Production Example 20 and Production Example 21were provided. Particle No. 27 and particle No. 28 were made as in <Step3-1> and <Step 3-2> of Production Example 8 except that these latexeswere used.

Production Example 29

Butadiene rubber polymer latex No. 1 prepared in <Step 1> of ProductionExample 1 was dried to obtain particle No. 29.

Production Examples 30 and 31

The reaction temperature after the introduction of the mixture of thematerials shown in the Component (3) column in Table 1 into theautoclave in <Step 1> of Production Example 1 was changed from 60° C. to80° C. or 45° C. Except for the change, butadiene rubber polymer latexeswere prepared as in <Step 1> of Production Example 1. Then, particle No.30 and particle No. 31 were made as in <Step 2> of Production Example 1except that these butadiene rubber polymer latexes were used.

Production Example 32

A polyethylene resin particle having a protrusion shape (trade name:FLO-THENE UF-4; manufactured by Sumitomo Seika Chemicals CompanyLimited) was subjected to corona treatment by a corona treatmentapparatus (APW-602F, manufactured by KASUGA DENKI, INC.) to obtain apolyethylene resin particle provided with hydrophilicity. Thepolyethylene resin particle will be also referred to as a“surface-treated polyethylene resin particle” below. 47 g of thesurface-treated polyethylene resin particle was introduced into 230 g ofa 10% by volume methanol solution of glycidyl methacrylate and dispersedto obtain a dispersion. The dispersion was stirred under a nitrogenatmosphere for 2 hours with the temperature kept at 50° C. Subsequently,the dispersion was filtered, and the filtered material was washed withmethanol. Then, filtration was performed again followed by vacuum dryingat a temperature of 60° C. for 10 hours. Thus, particle No. 32 havingglycidyl methacrylate chemically bonded to the surface (67 g) wasobtained.

TABLE 6 Parts by Material mass Component Corona-treated polyethyleneparticle 47 (20) 10 vol % glycidyl methacrylate/methanol solution 230

The outlines and physical properties (the primary particle diameter, thecircle-equivalent diameter of the aggregate, and the average degree ofunevenness) of particles Nos. 1 to 32 are shown in Table 7.

In addition, whether each particle is an aggregate of crosslinked rubberparticles or not is also shown together in Table 7. When the particle isan aggregate of crosslinked rubber particles, “A” of Aggregate is shown.When the particle is not an aggregate of crosslinked rubber particles,“S” of Single is shown.

TABLE 7 Particle Circle- State of Primary equivalent crosslinked Rubberypolymer (A) particle diameter of Average rubber particle ParticleButadiene Acrylic rubber Graft portion Graft ratio diameter aggregatedegree of A: Aggregate No. (Parts by mass) (Parts by mass) material % Bymass (nm) (μm) unevenness S: Single Production 1 1 25 — Acrylic 20 50025 1.20 A Example 2 2 25 — Acrylic 18 400 10 1.20 A 3 3 25 — Acrylic 23800 50 1.20 A 4 4 25 — Acrylic 15 200 25 1.05 A 5 5 25 — Acrylic 22 100025 1.35 A 6 6 25 — Acrylic 18 50 25 1.10 A 7 7 25 — Acrylic 28 1100 251.30 A 8 8 25 — Styrene acrylic 25 500 25 1.20 A 9 9 25 — Styreneacrylic 15 400 10 1.20 A 10 10 25 — Styrene acrylic 24 800 50 1.20 A 1111 25 — Styrene acrylic 22 200 25 1.05 A 12 12 25 — Styrene acrylic 231000 25 1.35 A 13 13 25 — Styrene acrylic 17 50 25 1.10 A 14 14 25 —Styrene acrylic 29 1100 25 1.30 A 15 15 — 25 Acrylic 22 400 25 1.20 A 1616 — 25 Acrylic 20 300 10 1.20 A 17 17 — 25 Acrylic 26 700 50 1.20 A 1818 — 25 Acrylic 18 100 25 1.05 A 19 19 — 25 Acrylic 24 800 25 1.35 A 2020 — 25 Acrylic 17 50 25 1.10 A 21 21 — 25 Acrylic 29 1100 25 1.30 A 2222 — 25 Styrene acrylic 22 400 25 1.20 A 23 23 — 25 Styrene acrylic 19300 10 1.20 A 24 24 — 25 Styrene acrylic 25 700 50 1.20 A 25 25 — 25Styrene acrylic 21 100 25 1.05 A 26 26 — 25 Styrene acrylic 23 800 251.35 A 27 27 — 25 Styrene acrylic 18 50 25 1.10 A 28 28 — 25 Styreneacrylic 26 1100 25 1.30 A 29 29 25 — None 0 500 25 1.20 A 30 30 25 —Acrylic 15 400 60 1.20 A 31 31 25 — Acrylic 12 400 8 1.20 A 32 32 *Polyethylene particle Acrylic 15 — 25 1.20 S

Example 1

1. Making of Electro-Conductive Rubber Composition

The materials shown in the following Table 8 were blended so that thetotal amount was 4.8 kg, and the blend was kneaded in a 6-liter kneader“TD6-15MDX” (trade name, manufactured by Toshin Co., Ltd.) adjusted to50° C. for 20 minutes to obtain a rubber composition.

TABLE 8 Parts by Material mass Medium high acrylonitrile-butadiene rubbe100 (trade name: N230SV; manufactured by JSR Corporation) Amount ofbonded acrylonitrile: 35.0%; Mooney viscosity (ML₁₊₄ 100° C.): 32;Specific gravity 0.98 Calcium carbonate (trade name: Silver W, 20manufactured by Shiraishi Kogyo Kaisha, Ltd.) Zinc stearate (trade name:SZ-2000, 1 manufactured by Sakai Chemical Industry Co., Ltd.) Zinc oxide(trade name: Zinc Oxide No. 2, 5 manufactured by Sakai Chemical IndustryCo., Ltd.) Carbon black (trade name: TOKABLACK #7360SB, 48 manufacturedby Tokai Carbon Co., Ltd.) Arithmetic mean particle diameter: 28 nm;Nitrogen adsorption specific surface area 77 m²/g; Amount of DBPabsorbed (A method): 87 cm³/100 g. Particle No. 1 75

To 100 parts by mass (4.0 kg) of the rubber composition, other materialsshown in the following Table 9 as vulcanizing agents were added, and themixture was kneaded by a 12-inch two-roll machine (manufactured byKANSAI ROLL Co., Ltd.) cooled to 20° C. for 10 minutes to make anelectro-conductive rubber composition 1.

TABLE 9 Parts by Material mass Rubber composition 100 Sulfur 1.0Vulcanization accelerator tetrabenzylthiuram disulfide 5.0 (trade name:SANCELER TBzTD, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)

2. Making of Charging Member

Next, an electro-conductive support (material: SUS material, length: 252mm, diameter: 6 mm) was provided. Using a crosshead extrusion apparatushaving a cylinder diameter of 70 mm (manufactured by MITSUBA MFG. CO.,LTD.), the electro-conductive rubber composition was extruded around theelectro-conductive support as the central axis to obtain an unvulcanizedrubber roller in which the outer periphery of the electro-conductivesupport was coated with a layer of the electro-conductive rubbercomposition. At the time, the thickness of the layer of theelectro-conductive rubber composition was adjusted to 1.5 mm, and theouter diameter of the unvulcanized rubber roller was adjusted to 9.0 mm.The unvulcanized rubber roller after the extrusion was heated in a hotair furnace at 170° C. for 1 hour to vulcanize the rubber, and then theends of the vulcanized rubber layer were removed to set the length ofthe rubber layer at 228 mm.

The outer peripheral surface of the obtained roller was polished using aplunge type rotary polishing machine (trade name: LEO-600-F4L-BME,manufactured by MINAKUCHI MACHINERY WORKS LTD.). A vitrified wheel wasused as the polishing grindstone, and the abrasive grain was greensilicon carbide GC, and the particle size was 100 mesh. The number ofrevolutions of the roller work was 350 rpm, and the number ofrevolutions of the polishing grindstone was 2000 rpm.

The rotation direction of the roller and the rotation direction of thepolishing grindstone were the same (the direction of being driven).Polishing was performed with the cutting speed set at 20 mm/min and thespark-out time (time at a cutting of 0 mm) set at 0 seconds, therebymaking charging member No. 1 in which the outer diameter of the centralportion of the roller in the longitudinal direction was 8.5 mm. Thethickness of the electro-conductive elastic layer was adjusted to 1.5mm. The grindstone shape was adjusted so that the amount of the crown(the difference between the outer diameter of the central portion andthe average value of outer diameters at positions each 90 mm away fromthe central portion in the directions of both ends) of the roller was120 μm.

A cross section of the obtained elastic layer was observed by atransmission electron microscope (trade name: H-7100FA, manufactured byHitachi High-Technologies Corporation), the projected area was obtained,and then the circle-equivalent diameter of the particle was calculated.As a result, the circle-equivalent diameter of particle No. 1 was 25 μm.

3. Image Evaluation with Charging Member

As an electrophotographic image forming apparatus for evaluation, amonochrome laser printer (trade name: LaserJet P4515n, manufactured byHP Japan Inc.) having the configuration illustrated in FIG. 5 wasprovided. In addition, one process cartridge for the above laser printerwas provided. The charging member No. 1 was mounted in the processcartridge. The charging member was allowed to abut theelectrophotographic photosensitive member with a pressing pressure of4.9 N at one end, 9.8 N in total at both ends, by springs.

Each process cartridge was loaded into the electrophotographic imageforming apparatus and adapted in an environment of a temperature of 5°C. and a relative humidity of for 24 hours. Subsequently, images wereoutput in the same environment. In image formation, an alternatingvoltage having a peak-to-peak voltage of 1800 V and a frequency of 2930Hz and a direct current voltage of −600 V were externally applied to thecharging member. In addition, the resolution of the images output was600 dpi. As the transfer material, letter size plain paper (trade name:XEROX 4024, manufactured by Fuji Xerox Co., Ltd.) was used.

The image output here was specifically an image in which horizontallines having a width of 2 dots in the direction perpendicular to therotation direction of the electrophotographic photosensitive member weredrawn at intervals of 176 dots in the rotation direction.

In addition, images were output in the so-called intermittent mode inwhich the rotation of the electrophotographic photosensitive member wasstopped for 3 seconds each time two images were continuously output.After 100 (0.1 K) images were output, after 10000 (10 K) images wereoutput, after 20000 (20 K) images were output, and after 30000 (30 K)images were output, a halftone image (an image in which horizontal lineshaving a width of 1 dot in the direction perpendicular to the rotationdirection of the photosensitive member were drawn at intervals of 2 dotsin the rotation direction) was output. The four halftone images obtainedwere visually observed and evaluated according to the followingcriteria:

Rank A: No density unevenness occurs in any of the four halftone images.

Rank B: Only slight density unevenness is noted in any one of the fourhalftone images.

Rank C: Density unevenness is confirmed in at least one of the fourhalftone images.

Rank D: Density unevenness is conspicuous and a decrease in imagequality is noted in at least one of the four halftone images.

4. Evaluation with Cleanerless Mechanism

The process cartridge of the monochrome laser printer was converted asfollows: a gear such that the charging portion roller rotated in theforward direction with respect to the rotation of the photosensitivedrum with a peripheral speed difference of 10% was attached, and thecleaning blade was removed. Charging member No. 1 was incorporated intothe converted process cartridge, and 1000 images were output as in theabove “3. Image Evaluation with Charging Member” using the monochromelaser printer. Subsequently, charging member No. 1 was removed from theprocess cartridge, and the contamination of the charging member wasevaluated by the following method.

A polyester adhesive tape (trade name: No. 31B; manufactured by NittoDenko Corporation, thickness=0.053 mm, peel adhesion=5.6 N/19 mm,tensile strength=115 N/19 mm, elongation=100%) was affixed to thesurface of the entire image printing region of the charging roller, andthe adhesive tape was peeled together with contamination adhering to thesurface of the charging roller, and affixed to letter size plain paper(trade name: XEROX 4024, manufactured by Fuji Xerox Co., Ltd.).

The reflection density of the adhesive tape was measured by aphotovoltaic reflection densitometer (trade name: TC-6DS/A, manufacturedby Tokyo Denshoku Co., Ltd.) for the entire image printing region, andthe maximum value Cmax was obtained. Next, the reflection density of anunused polyester tape also affixed to the letter size plain paper wasmeasured, and the minimum value Cmin was obtained, and the differencebetween both values, “ΔC=Cmax−Cmin,” was adopted as “the value ofcoloring density.” The smaller the value of coloring density is, thesmaller the amount of contamination on the surface of the chargingmember is. Therefore, the value of coloring density was taken as anindicator of the contamination of the charging member in the cleanerlesssystem. The evaluation result is shown in Table 10.

Examples 2 to 52

In Example 1, the type of the aggregate of the crosslinked rubberparticles and the amount of the aggregate of the crosslinked rubberparticles used were changed, and the polishing conditions such as aspark-out time in a polishing process and a number of revolutions of awork to be polished, i.e. a roller were adjusted as shown in Tables 10to 13, and changed the average height of the protrusion. Except forthese, charging members were made and evaluation was performed as inExample 1. The charging roller production conditions and evaluationresults are shown in Tables 10 to 13. The circle-equivalent diameter isalso shown in Table 7

Comparative Example 1

In Example 1, the aggregate of the crosslinked rubber particles was notadded. Except for this, a charging members was made and evaluation wasperformed as in Example 1. The charging member production conditions andevaluation results are shown in Table 14.

Comparative Examples 2 to 4

In Example 1, the type of the aggregate of the crosslinked rubberparticles and the amount of the aggregate of the crosslinked rubberparticles used were changed, and the polishing conditions were adjustedto change the average height of the protrusion. Except for these,charging members were made and evaluation was performed as in Example 1.The charging member production conditions and evaluation results areshown in Table 14.

Comparative Examples 5 and 6

Charging members were made and evaluation was performed as in Example 1except that in Example 1, the polishing conditions were adjusted tochange the average height of the protrusion. The charging memberproduction conditions and evaluation results are shown in Table 14.

Comparative Examples 7 and 8

Charging members were made and evaluation was performed as in Example 1except that in Example 1, the number of parts of the aggregate of thecrosslinked rubber particles added was changed. The charging memberproduction conditions and evaluation results are shown in Table 14.

Comparative Example 9

A Charging member was made and evaluation was performed as in Example 1except that in Example 1, the aggregate of the crosslinked rubberparticles was changed to the particle obtained in Production Example 32(a particle that was not an aggregate of crosslinked rubber particles).The charging member production conditions and evaluation results areshown in Table 14.

[Consideration of Evaluation Results]

Examples 1 to 13 are Examples using an aggregate of crosslinked rubberparticles in which an acrylic resin is chemically bonded to the surfaceof a butadiene rubber particle and are the same except that the primaryparticle diameter, the circle-equivalent diameter, the average height ofthe protrusion, the average degree of unevenness, the polishingconditions (the polishing time (spark-out time)) and the amount addedare changed. Examples 14 to 26 are each an Example using an aggregate ofcrosslinked rubber particles in which a styrene acrylic resin ischemically bonded to the surface of a butadiene rubber particle.Examples 27 to 39 are Examples using an aggregate of crosslinked rubberparticles in which an acrylic resin is chemically bonded to the surfaceof an acrylic rubber particle. Examples 40 to 52 are Examples using anaggregate of crosslinked rubber particles in which a styrene acrylicresin is chemically bonded to the surface of an acrylic rubber particle.In the above Examples 1 to 52, in the image evaluation, both in theinitial image and in the image after endurance, contamination due to theadhesion of an external additive and toner to the charging member wassuppressed, and the durability was excellent in image formation.

On the other hand, in Comparative Example 1, an aggregate of crosslinkedrubber particles was not contained, and therefore a large amount oftransfer residual toner adhered to the charging member, and the imageforming properties were insufficient. For Comparative Examples 2 to 8,any one or more of the circle-equivalent diameter of the aggregate ofthe crosslinked rubber particles, the average height of the protrusion,and the amount added were outside the scope of the present invention,the durability was insufficient in image formation, and thecontamination resistance of the cleanerless system was alsoinsufficient. In Comparative Example 9, contamination adhering to theprotrusion derived from the resin particle could not be incorporatedinto the resin particle, and therefore a large amount of transferresidual toner adhered to the charging member, and the image formingproperties were insufficient.

TABLE 10 Example 1 2 3 4 5 6 7 Elastic layer NBR NBR NBR NBR NBR NBR NBRParticle Particle No. 1 2 2 2 2 3 3 Graft portion Acrylic AcrylicAcrylic Acrylic Acrylic Acrylic Acrylic Butadiene Parts 25 25 25 25 2525 25 Primary particle diameter nm 500 400 400 400 400 800 800Circle-equivalent μm 25 10 10 10 10 50 50 diameter Average degree ofunevenness 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Content ratio in electro-% by mass 30 10 50 50 10 10 50 conductive elastic layer Number ofrevolutions of polishing rpm 350 350 350 350 350 350 350 work Spark-outtime in polishing process sec 2.5 5.0 5.0 1.0 1.0 5.0 5.0 Average heightof protrusion nm 100 50 50 200 200 50 50 derived from crosslinked rubberparticles on surface of charging member Image evaluation VDG 0.1K A A AA A A A VDG 10K A A B B A A A VDG 20K A B B B A B B VDG 30K A B B B A BB Contamination evaluation ΔC 10.5 10.2 12.5 13.0 12.0 11.1 12.1 Example8 9 10 11 12 13 Elastic layer NBR NBR NBR NBR NBR NBR Particle ParticleNo. 3 3 4 5 6 7 Graft portion Acrylic Acrylic Acrylic Acrylic AcrylicAcrylic Butadiene Parts 25 25 25 25 25 25 Primary particle diameter nm800 800 200 1000 50 1100 Circle-equivalent μm 50 50 25 25 25 25 diameterAverage degree of unevenness 1.20 1.20 1.05 1.35 1.10 1.30 Content ratioin electro- % by mass 50 10 30 30 30 30 conductive elastic layer Numberof revolutions of polishing rpm 350 350 350 350 350 350 work Spark-outtime in polishing process sec 1.0 1.0 1.0 1.0 1.0 1.0 Average height ofprotrusion nm 200 200 200 200 200 200 derived from crosslinked rubberparticles on surface of charging member Image evaluation VDG 0.1K A A AA A A VDG 10K A A B B B B VDG 20K B A B B B B VDG 30K B A B B B BContamination evaluation ΔC 12.8 11.5 18.0 17.6 18.6 19.6

TABLE 11 Example 14 15 16 17 18 19 20 Elastic layer NBR NBR NBR NBR NBRNBR NBR Particle Particle No. 8 9 9 9 9 10 10 Graft portion StyreneStyrene Styrene Styrene Styrene Styrene Styrene acrylic acrylic acrylicacrylic acrylic acrylic acrylic Butadiene Parts 25 25 25 25 25 25 25Primary nm 500 400 400 400 400 800 800 particle diameter Circle- μm 2510 10 10 10 50 50 equivalent diameter Average degree of unevenness 1.201.20 1.20 1.20 1.20 1.20 1.20 Content ratio in % by mass 30 10 50 50 1010 50 electro- conductive elastic layer Number of revolutions of rpm 350350 350 350 350 350 350 polishing work Spark-out time in sec 2.5 5.0 5.01.0 1.0 5.0 5.0 polishing process Average height of nm 100 50 50 200 20050 50 protrusion derived from crosslinked rubber particles on surface ofcharging member Image evaluation VDG 0.1K A A A A A A A VDG 10K A A B BA A A VDG 20K A B B B A B B VDG 30K A B B B A B B Contaminationevaluation ΔC 9.7 9.5 11.1 11.2 10 9.9 10.9 Example 21 22 23 24 25 26Elastic layer NBR NBR NBR NBR NBR NBR Particle Particle No. 10 10 11 1213 14 Graft portion Styrene Styrene Styrene Styrene Styrene Styreneacrylic acrylic acrylic acrylic acrylic acrylic Butadiene Parts 25 25 2525 25 25 Primary nm 800 800 200 1000 50 1100 particle diameter Circle-μm 50 50 25 25 25 25 equivalent diameter Average degree of unevenness1.20 1.20 1.05 1.35 1.10 1.30 Content ratio in % by mass 50 10 30 30 3030 electro- conductive elastic layer Number of revolutions of rpm 350350 350 350 350 350 polishing work Spark-out time in sec 1.0 1.0 1.0 1.01.0 1.0 polishing process Average height of nm 200 200 200 200 200 200protrusion derived from crosslinked rubber particles on surface ofcharging member Image evaluation VDG 0.1K A A A A A A VDG 10K A A B B BB VDG 20K B A B B B B VDG 30K B A B B B B Contamination evaluation ΔC12.0 10.5 14.3 14.1 15.1 16.1

TABLE 12 Example 27 28 29 30 31 32 33 Elastic layer NBR NBR NBR NBR NBRNBR NBR Particle Particle No. 15 16 16 16 16 17 17 Graft portion AcrylicAcrylic Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic rubber Parts 2525 25 25 25 25 25 Primary particle nm 400 300 300 300 300 700 700diameter Circle- μm 25 10 10 10 10 50 50 equivalent diameter Averagedegree of unevenness 1.20 1.20 1.20 1.20 1.20 1.20 1.20 Content ratio in% by mass 30 10 50 50 10 10 50 electro- conductive elastic layer Numberof revolutions of rpm 350 350 350 350 350 350 350 polishing workSpark-out time in polishing sec 2.5 5.0 5.0 1.0 1.0 5.0 5.0 processAverage height of nm 100 50 50 200 200 50 50 protrusion derived fromcrosslinked rubber particles on surface of charging member Imageevaluation VDG 0.1K A A A A A A A VDG 10K A A B B A A A VDG 20K A B B BA B B VDG 30K A B B B A B B Contamination evaluation ΔC 11.3 12 11.512.6 12.6 12.8 13.5 Example 34 35 36 37 38 39 Elastic layer NBR NBR NBRNBR NBR NBR Particle Particle No. 17 17 18 19 20 21 Graft portionAcrylic Acrylic Acrylic Acrylic Acrylic Acrylic Acrylic rubber Parts 2525 25 25 25 25 Primary particle nm 700 700 100 800 50 1100 diameterCircle- μm 50 50 25 25 25 25 equivalent diameter Average degree ofunevenness 1.20 1.20 1.05 1.35 1.10 1.30 Content ratio in % by mass 5010 30 30 30 30 electro- conductive elastic layer Number of revolutionsof rpm 350 350 350 350 350 350 polishing work Spark-out time inpolishing sec 1.0 1.0 1.0 1.0 1.0 1.0 process Average height of nm 200200 200 200 200 200 protrusion derived from crosslinked rubber particleson surface of charging member Image evaluation VDG 0.1K A A A A A A VDG10K A A B B B B VDG 20K B A B B B B VDG 30K B A B B B B Contaminationevaluation ΔC 14.0 12.1 18.5 18.0 19.0 20.0

TABLE 13 Example 40 41 42 43 44 45 46 Elastic layer NBR NBR NBR NBR NBRNBR NBR Particle Particle No. 22 23 23 23 23 24 24 Graft portion StyreneStyrene Styrene Styrene Styrene Styrene Styrene acrylic acrylic acrylicacrylic acrylic acrylic acrylic Acrylic rubber Parts 25 25 25 25 25 2525 Primary nm 400 300 300 300 300 700 700 particle diameter Circle- μm25 10 10 10 10 50 50 equivalent diameter Average degree of unevenness1.20 1.20 1.20 1.20 1.20 1.20 1.20 Content ratio in % by mass 30 10 5050 10 10 50 electro- conductive elastic layer Number of revolutions ofrpm 350 350 350 350 350 350 350 polishing work Spark-out time in sec 2.55.0 5.0 1.0 1.0 5.0 5.0 polishing process Average height of nm 100 50 50200 200 50 50 protrusion derived from crosslinked rubber particles onsurface of charging member Image evaluation VDG 0.1K A A A A A A A VDG10K A A B B A A A VDG 20K A B B B A B B VDG 30K A B B B A B BContamination evaluation ΔC 10.0 10.2 12.5 11.9 9.9 10.1 12.4 Example 4748 49 50 51 52 Elastic layer NBR NBR NBR NBR NBR NBR Particle ParticleNo. 24 24 25 26 27 28 Graft portion Styrene Styrene Styrene StyreneStyrene Styrene acrylic acrylic acrylic acrylic acrylic acrylic Acrylicrubber Parts 25 25 25 25 25 25 Primary nm 700 700 100 800 50 1100particle diameter Circle- μm 50 50 25 25 25 25 equivalent diameterAverage degree of unevenness 1.20 1.20 1.05 1.35 1.10 1.30 Content ratioin % by mass 50 10 30 30 30 30 electro- conductive elastic layer Numberof revolutions of rpm 350 350 350 350 350 350 polishing work Spark-outtime in sec 1.0 1.0 1.0 1.0 1.0 1.0 polishing process Average height ofnm 200 200 200 200 200 200 protrusion derived from crosslinked rubberparticles on surface of charging member Image evaluation VDG 0.1K A A AA A A VDG 10K A A B B B B VDG 20K B A B B B B VDG 30K B A B B B BContamination evaluation ΔC 12.2 9.5 13.9 14.6 15.6 16.6

TABLE 14 Comparative Example 1 2 3 4 5 6 7 8 9 Elastic layer NBR NBR NBRNBR NBR NBR NBR NBR NBR Particle Particle No. — 29 30 31 1 1 1 1 32Graft portion — None Acrylic Acrylic Acrylic Acrylic Acrylic AcrylicAcrylic Butadiene Parts — 25 25 25 25 25 25 25 25 Primary particle nm —500 400 400 500 500 500 500 — diameter Circle- μm — 25 60 8 25 25 25 2525 equivalent diameter Average degree of unevenness 1.20 1.20 1.20 1.201.20 1.20 1.20 1.20 Content ratio in % by mass — 30 30 30 30 30 8 51 30electro-conductive elastic layer Number of revolutions of rpm 350 350350 350 350 350 350 350 350 polishing work Spark-out time in polishingsec 0.0 2.5 0.0 5.0 0.0 10.0 2.5 2.5 2.5 process Average height of nm —100 250 50 250 30 100 100 100 protrusion derived from particle oncharging member surface Image evaluation VDG 0.1K A A A A A A A A A VDG10K C B B B B B B B B VDG 20K D C C C C C C C C VDG 30K D C C C C C C CD Contamination evaluation ΔC 59.8 35.5 39.8 41.5 31.5 36.1 41.2 39.545.5

While the present invention has been described with reference toexemplary embodiments, it is to be understood that the invention is notlimited to the disclosed exemplary embodiments. The scope of thefollowing claims is to be accorded the broadest interpretation so as toencompass all such modifications and equivalent structures andfunctions.

This application claims the benefit of Japanese Patent Application No.2015-193134, filed Sep. 30, 2015 which is hereby incorporated byreference herein in its entirety.

What is claimed is:
 1. A charging member comprising: anelectro-conductive support; and an electro-conductive elastic layer onthe electro-conductive support, wherein the electro-conductive elasticlayer comprises 10% by mass or more and 50% by mass or less of anaggregate of crosslinked rubber particles, the aggregate of thecrosslinked rubber particles has a circle-equivalent diameter of 10 μmor more and 50 μm or less, the crosslinked rubber particles have one ofan acrylic resin and a styrene acrylic resin chemically bonded to asurface thereof, the charging member comprises protrusions derived fromthe aggregate of the crosslinked rubber particles on a surface thereof,and the protrusions have an average height of 50 nm or more and 200 nmor less.
 2. The charging member according to claim 1, wherein theaverage height of the protrusion are 100 nm or more and 200 nm or less.3. The charging member according to claim 1, wherein a primary particlediameter of the crosslinked rubber particles is 100 nm or more and 1000nm or less.
 4. The charging member according to claim 1, wherein arubber of the crosslinked rubber particles is at least one selected fromthe group consisting of an acrylonitrile rubber and a styrene-butadienerubber.
 5. The charging member according to claim 1, wherein an averagedegree of unevenness of a surface of the aggregate of the crosslinkedrubber particles is 1.10 or more and 1.30 or less.
 6. Anelectrophotographic image forming apparatus comprising anelectrophotographic photosensitive member and a charging member disposedin contact with the electrophotographic photosensitive member, whereinthe charging member is a charging member comprising: anelectro-conductive support; and an electro-conductive elastic layer onthe electro-conductive support, wherein the electro-conductive elasticlayer comprises 10% by mass or more and 50% by mass or less of anaggregate of crosslinked rubber particles, the aggregate of thecrosslinked rubber particles has a circle-equivalent diameter of 10 μmor more and 50 μm or less, the crosslinked rubber particles have one ofan acrylic resin and a styrene acrylic resin chemically bonded to asurface thereof, the charging member comprises protrusions derived fromthe aggregate of the crosslinked rubber particles on a surface thereof,and the protrusions have an average height of 50 nm or more and 200 nmor less.
 7. A process cartridge configured to be attachable to anddetachable from a main body of an electrophotographic image formingapparatus, comprising an electrophotographic photosensitive member and acharging member disposed in contact with the electrophotographicphotosensitive member, wherein the charging member is a charging membercomprising: an electro-conductive support; and an electro-conductiveelastic layer on the electro-conductive support, wherein theelectro-conductive elastic layer comprises 10% by mass or more and 50%by mass or less of an aggregate of a crosslinked rubber particles, theaggregate of the crosslinked rubber particles has a circle-equivalentdiameter of 10 μm or more and 50 μm or less, the crosslinked rubberparticles have one of an acrylic resin and a styrene acrylic resinchemically bonded to a surface thereof, the charging member comprisesprotrusions derived from the aggregate of the crosslinked rubberparticles on a surface thereof, and the protrusions have an averageheight of 50 nm or more and 200 nm or less.